Method of printing cellulosic fiber materials without an additional fixing process step

ABSTRACT

Reactive dyes of formula 
                 
 
wherein A is the radical of a monoazo, polyazo, metal complex azo, anthraquinone, phthalocyanine, formazan or dioxazine chromophore, R 1 , R 2  and R 3  are each hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, X 1  and X 2  are halogen, B is an organic bridging member, T is a reactive radical as defined herein and V 1  and V 2  are each independently of the other N, C—H, C—Cl or C—F, give prints that are distinguished by brilliant color shades and good all-round properties.

This application is a continuation of application Ser. No. 09/899,439,filed Jul. 5, 2001, now U.S. Pat. No. 6,623,533.

The present invention relates to a simplified method of printingcellulosic fibre materials in which a separate fixing process, such asthe steaming of the printed fibre material, is superfluous. The methodis simplified by the use of certain reactive dyes which aredistinguished by at least three fibre-reactive groups, at least two ofthe said fibre-reactive groups being halotriazinyl radicals and at leastone being especially of the vinylsulfonyl type. The present inventionrelates also to the novel reactive dyes.

Methods of printing cellulosic fibre materials have been known for along time. The class of the reactive dyes has been successful in theface of the ever increasing demands in terms of colour fastness. Inprinting procedures on cellulose fibres that employ reactive dyes, useis made of the particularly stable covalent binding of the dyes to thehydroxy groups of the fibres. The binding of the reactive dyes to thefibres (fixing) is carried out in alkaline medium and requires treatmentof the printed fibre material in a separate fixing process, which isusually carried out with saturated steam at relatively high temperatures(steaming), in order to achieve uniform and optimum fixing of the dye.In the hitherto known methods, such a treatment requires an additionaldevice in which the necessary fixing heat and the steam are generated.There is accordingly a need for a simplified printing method that can beused on an industrial scale in which the additional process step offixing the dye does not need to be carried out and in which uniform andoptimum fixing is, for example, achieved directly on drying the printedfibre material. The advantage of such a simplified method is especiallythat expenditure in terms of time and cost is distinctly lower than inthe case of the hitherto customary printing methods, since it ispossible to omit the additional process step of fixing the dye and thusdispense with the additional fixing device.

The present invention accordingly relates to a method of printingcellulosic fibre materials in which the fibre material is brought intocontact with reactive dyes of formula

wherein

-   A is the radical of a monoazo, polyazo, metal complex azo,    anthraquinone, phthalocyanine, formazan or dioxazine chromophore,-   R₁, R₂ and R₃ are each independently of the others hydrogen or    unsubstituted or substituted-   C₁-C₄alkyl,-   X₁ and X₂ are halogen,-   B is an organic bridging member,-   T is a reactive radical of formula-   R₄ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy,    sulfo, sulfato, carboxy or by cyano, or a radical    wherein R₅ is as defined hereinbelow,-   R₅ is hydrogen, hydroxy, sulfo, sulfato, carboxy, cyano, halogen,    C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy, carbamoyl or a group —SO₂—Y,-   R₆ is hydrogen or C₁-C₄alkyl,-   alk and alk₁ are each independently of the other linear or branched    C₁-C₆alkylene,-   arylene is an unsubstituted or sulfo-, carboxy-, hydroxy-,    C₁-C₄alkyl-, C₁-C₄alkbxy- or halo-substituted phenylene or    naphthylene radical,-   Y is vinyl or a radical —CH₂—CH₂—U and U is a leaving group,-   Y₁ is a group —CH(Hal)—CH₂(Hal) or —C(Hal)═CH₂, wherein Hal is    chlorine or bromine,-   W is a group —SO₂—NR₆—, —CONR₆— or —NR₆CO—, wherein R₆ is as defined    hereinabove,-   Q is a radical —O— or —NR₆—, wherein R₆ is as defined hereinabove,-   n is the number 0 or 1, and-   V₁ and V₂ are each independently of the other N, C—H, C—Cl or C—F,    and the fixing of the printed fibre material is carried out without    an additional fixing process step.

Within the context of the present invention, “an additional fixingprocess step” denotes th treatment of the fibre material, after theprinting and after the drying immediately subsequent thereto, in aseparate fixing device at relatively high temperatures, which step isusually carried out in the presence of saturated steam (steaming).

According to the invention, the fixing of the dye on the fibre materialhas already been achieved immediately after the printing and also thedrying of the fibre material, which is to be carried out anyway.

Preferably, the method according to the invention is carried outindustrially on a large scale.

As alkyl radicals in the reactive dye of formula (1), the radicals R₁,R₂ and R₃ are straight-chain or branched. The alkyl radicals may befurther substituted, for example by hydroxy, sulfo, sulfato, cyano orcarboxy. The following radicals may be mentioned as examples: methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, andthe corresponding radicals substituted by hydroxy, sulfo, sulfato, cyanoor carboxy. Preferred substituents are hydroxy, sulfo or sulfato,especially hydroxy or sulfato and preferably hydroxy.

Preferably, R₁ is hydrogen or C₁-C₄alkyl, especially hydrogen.

R₂ and R₃ are preferably each independently of the other hydrogen, orC₁-C₄alkyl unsubstituted or substituted by hydroxy, sulfo, sulfato,cyano or by carboxy. According to one embodiment of interest, one of theradicals R₂ and R₃ is C₁-C₄alkyl substituted by hydroxy, sulfo, sulfato,cyano or by carboxy, especially by hydroxy, and the other of theradicals R₂ and R₃ is hydrogen or C₁-C₄alkyl, especially hydrogen.

Especially preferably, R₂ and R₃ are each independently of the otherhydrogen or C₁-C₄alkyl, especially hydrogen.

X₁ and X₂ are, for example, chlorine, fluorine or bromine.

X₁ and X₂ are preferably each independently of the other chlorine orfluorine. Especially preferably, one of the radicals X₁ and X₂ isfluorine and the other is chlorine, or X₁ and X₂ are both fluorine. Moreespecially, one of the radicals X₁ and X₂ is fluorine and the other ischlorine.

V₁ and V₂ are preferably N.

The organic bridging member B may be, for example, an aliphatic,cycloaliphatic, aromatic or araliphatic bridging member.

As an aliphatic bridging member, B is, for example, a straight-chain orbranched C₂-C₁₂-alkylene radical, especially a C₂-C₆alkylene radical,that may be interrupted by 1, 2 or 3 members from the group —NH—,—N(CH₃)— and especially —O— and that is unsubstituted or substituted byhydroxy, sulfo, sulfato, cyano or by carboxy. Hydroxy, sulfo or sulfato,especially hydroxy or sulfato, are preferred as substituents of thealkylene radicals mentioned for B.

As aliphatic bridging members for B there come into consideration also,for example, C₅-C₉-cycloalkylene radicals, especially cyclohexyleneradicals. The said cycloalkylene radicals may be unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylarnino, sulfo,halogen or carboxy, especially by C₁-C₄alkyl. As aliphatic bridgingmembers for B there may also be mentioned methylenecyclohexylene,ethylenecyclohexylene and methylenecyclo-hexylenemethylene radicalsunsubstituted or substituted in the cyclohexylene ring by C₁-C₄-alkyl,especially methyl.

For the radical of formula

there comes into consideration, for example, also a radical of formula

wherein alk is C₁-C₄alkylene, for example ethylene.

As an aromatic bridging member, B is, for example, unsubstituted orC₁-C₄alkyl-, C₂-C₄-alkoxy-, C₂-C₄alkanoylamino-, sulfo-, halo- orcarboxy-substituted C₁-C₆alkylenephenyl ne, for examplemethylenephenylene, C₁-C₄alkylenephenylene-C₁-C₄alkylene, for examplemethylenephenylenemethylene, or phenylene, or a radical of formula

wherein the benzene rings I and II are unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄-alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or bycarboxy and L is a direct bond or a C₂-C₁₀-alkylene radical that may beinterrupted by 1, 2 or 3 oxygen atoms, or L is a bridging member offormula —CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂—, —NH—CO—NH—, —O—,—S— or SO₂—. As an aromatic bridging member, B is preferably phenylenethat may be substituted as indicated above. Preferably, the aromaticbridging members mentioned for B are unsubstituted or sulfo-substituted.

Examples of aromatic bridging members B are 1,3-phenylene,1,4-phenylene, 4-methyl-1,3-phenylene, 4-sulfo-1,3-phenylene,3-sulfo-1,4-phenylene, 3,6-disulfo-1,4-phenylen,4,6-disulfo-1,3-phenylene, 3,7-disulfo-1,5-naphthylene,4,8disulfo-2,6-naphthylene, 2,2′disulfo-4,4′-diphenylene,4,4′-phenyleneurea-2,2′-disulfonic acid and2,2′-disulfo-4,4′-stilbenylene.

B is preferably a C₂-C₁₂alkylene radical that may be interrupted by 1, 2or 3 members from the group —NH—, —N(CH₃)— or —O— and that isunsubstituted or substituted by hydroxy, sulfo, sulfato, cyano orcarboxy;

an unsubstituted or C₁-C₄alkyl-, C₁-C₄alkoxy-, C₂-C₄alkanoylamino-,sulfo-, halo- or carboxy-substituted C₅-C₉cycloalkylene radical,C₁-C₆alkylenephenylene radical or phenylene radical;

or the radical of formula

is a radical of formula

B is especially a C₂-C₁₂alkylene radical that may be interrupted by 1, 2or 3 members —O— and that is unsubstituted or substituted by hydroxy,sulfo, sulfato, cyano or by carboxy, or is a phenylene radical that isunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄-alkanoylamino, sulfo, halogen or by carboxy.

B is more especially a C₂-C₁₂alkylene radical, especially aC₂-C₆alkylene radical, for example 1,2-ethylene, 1,3-propylene,1,2-propylene, 1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene,1,6-hexylene, 2,5-hexylene, 4,6-hexylene or a radical of formula

that may be interrupted by 1, 2 or 3 members —O— and that isunsubstituted or substituted by hydroxy or by sulfato, but preferablythat is not interrupted by —O—.

Of particular importance as bridging members B are those of formula—CH₂—CH(R₇)— wherein R₇ is C₁-C₄alkyl, especially methyl, and especially1,2-propylene.

Of particular importance also, as the radical

is a radical of formula

When Y is a radical —CH₂—CH₂—U, the leaving group U may be, for example,—Cl, —Br, —F, —OSO₃H, —SSO₃H, —OCO—CH₃, OPO₃H₂, —OCO—C₆H₅,OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂. Preferably, U is a group offormula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃, —OCO—C₆H₅ or —OPO₃H₂, especially—Cl or —OSO₃H and more especially —OSO₃H.

Y is preferably vinyl, β-chloroethyl, β-sulfatoethyl,β-thiosulfatoethyi, β-acetoxyethyl, β-phenoxyethyl or β-phosphatoethyland especially β-sulfatoethyl or vinyl.

Hal is preferably bromine.

alk and alk₁ are each independently of the other, for example,methylene, 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene,1,6-hexylene or a branched isomer thereof, alk and alk₁ are eachindependently of the other preferably a C₁-C₄alkylene radical andespecially an ethylene or propylene radical.

Preferred meanings of arylene are an unsubstituted or sulfo-, methyl-,methoxy- or carboxy-substituted 1,3- or 1,4-phenylene radical andespecially an unsubstituted 1,3- or 1,4-phenylene radical.

R₄ is preferably hydrogen, C₁-C₄alkyl or a radical of formula

wherein R₅, Y and alk each have the definitions and preferred meaningsgiven hereinabove. R₄ is especially hydrogen, methyl or ethyl and moreespecially hydrogen.

R₅ is preferably hydrogen.

R₆ is preferably hydrogen, methyl or ethyl and especially hydrogen.

The variable Q is preferably —NH— or —O— and especially —O—.

W is preferably a group of formula —CONH— or —NHCO—, especially a groupof formula —CONH—.

The variable n is preferably the number 0.

Preferred reactive radicals T of formulae (2a) to (2f) are those whereinR₄, R₅ and R₆ are each hydrogen, Q is the radical —NH— or —O—, W is agroup —CONH—, alk and alk₁ are each independently of the other ethyleneor propylene, arylene is unsubstituted or methyl-, methoxy-, carboxy- orsulfo-substituted phenylene, Y is vinyl, β-chloroethyl orβ-sulfatoethyl, especially vinyl or β-sulfatoethyl, Y₁ is —CHBr—CH₂Br or—CBr═CH₂ and n is the number 0, the, radicals of formulae (2c) and (2d)being especially preferred.

T is more especially a group of formula

especially (2c′), in which formulae Y has the definitions and preferredmeanings given hereinabove.

An especially important reactive radical T is the radical of formula

wherein Y is vinyl or β-sulfatoethyl.

When A is the radical of a monoazo, polyazo or metal complex azochromophore, the following, especially, come into consideration:

chromophore radicals of a monoazo or disazo dye of formulaD-N═N—(M—N═N)_(u)—K—  (4) or-D-N═N—(M—N═N)_(u)—K  (5),wherein D is the radical of a diazo component of the benzene ornaphthalene series, M is the radical of a central component of thebenzene or naphthalene series, K is the radical of a coupling componentof the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one oracetoacetic acid arylamide series and u is the number 0 or 1, andwherein D, M and K may carry substituents customary for azo dyes, forexample C₁-C₄alkyl or C₁-C₄alkoxy each unsubstituted or furthersubstituted by hydroxy, sulfo or by sulfato; halogen, carboxy, sulfo,nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido,hydroxy, carboxy, sulfomethyl, C₂-C₄alkanoylamino; benzoylaminounsubstituted or substituted in the phenyl ring by C₁-C₄alkyl,C₁-C₄alkoxy, halogen or by sulfo; phenyl unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo; andfibre-reactive radicals. There also come into consideration the metalcomplexes derived from the dye radicals of formulae (4) and (5), suchdye radicals being especially those of a 1:1 copper complex azo dye or1:2 chromium complex azo dye of the benzene or naphthalene series,wherein the copper or chromium atom, as the case may be, is bonded to ametallisable group in the ortho position on both sides of the azobridge.

When the chromophore radicals of formula (4) or (5) carry a reactiveradical, the reactive radical may be, for example, of formula

 —SO₂—Y  (6a),—CONH—(CH₂)_(m)—SO₂—Y  (6b),—CONH—(CH₂)_(l)—O—(CH₂)_(m)SO₂—Y  (6c),—(O)_(p)—(CH₂)_(q)—CONH—(CH₂)_(m)—SO₂—Y  (6d),—NH—CO—CH(Hal)—CH₂(Hal)  (6e),

—NH—CO—C(Hal)═CH₂  (6f) or

in which formulae Y and Hal each have the definitions and preferredmeanings given hereinabove, T₁ independently has the definitions andpreferred meanings given hereinabove for T, X₂′ independently has thedefinitions and preferred meanings given hereinabove for X₂, R₃′independently has the definitions and preferred meanings givenhereinabove for R₃, p is the number 0 or 1 and l, m and q are eachindependently of the others an integer from 1 to 6. Preferably, p is thenumber 0, l and m are each independently of the other 2 or 3 and q is thnumber 1, 2, 3 or 4.

When the chromophore radicals of formula (4) or (5) carry a reactiveradical, the reactive radical preferably corresponds to the aboveformula (6a) or (6g).

Preferably, the chromophore radicals of formula (4) or (5) do not carrya reactive radical.

Especially preferred radicals of a monoazo or disazo chromophore A areas follows:

in which formulae (R₈)₀₋₃ denotes from 0 to 3 identical or differentsubstituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyand sulfo,

wherein (R₉)₀₋₄ denotes from 0 to 4 identical or different substituentsfrom the group halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy, amino, acetyl-amino, ureido,hydroxy, carboxy, sulfomethyl and sulfo,

in which formulae R₁₀ is hydrogen, C₁-C₄alkanoyl, benzoyl or ahalotriazinyl radical of the above-indicated formula (6g),

in which formulae (R₁₁)₀₋₃ denotes from 0 to 3 identical or differentsubstituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyand sulfo,

wherein R₁₂ and R₁₄ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl and R₁₃ is hydrogen, cyano, carbamoyl orsulfomethyl,

wherein (R₁₅)₀₋₂ denotes from 0 to 2 identical or different substituentsfrom the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo; andY is as defined hereinabove,

wherein (R₁₆)₀₋₂ denotes from 0 to 2 identical or different substituentsfrom the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy and sulfo, andY has the definitions given hereinabove,

in which formulae (R₈)₀₋₃ denotes from 0 to 3 identical or differentsubstituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyand sulfo, (R₈′)₀₋₃ denotes from 0 to 3 identical or differentsubstituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, acetylamino,halogen, carboxy, sulfo, C₁-C₄hydroxyalkoxy and C₁-C₄sulfatoalkoxy,(R₉)₀₋₃ denotes from 0 to 3 identical or different substituents from thegroup halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,C₁-C₄alkyl, C₁-C₄alkoxy, amino, acetylamino, ureido, hydroxy, carboxy,sulfomethyl and sulfo, (R₁₀′)₀₋₃ denotes from 0 to 3 identical ordifferent substituents from the group C₁-C₄alkyl, C₁-C₄alkoxy, halogen,carboxy and sulfo, and Y is as defined hereinabove.

The radicals of formulae (7a) to (7s) may carry in the phenyl ornaphthyl rings, as a further substituent, also a radical of formula—SO₂Y, wherein Y is as defined hereinabove. Pr ferably they do notcontain a radical of formula —SO₂Y.

The radical of a formazan dye A is preferably a dye radical of formula

wherein the benzene nuclei do not contain, any further substituents orare further substituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkylsulfonyl,halogen or carboxy.

As a radical of a phthalocyanine dye, A is preferably a radical offormula

wherein Pc is the radical of a metal phthalocyanine, especially theradical of a copper or nickel phthalocyanine; R is —OH and/or —NR₁₈R₁₉;R₁₈ and R₁₉ are each independ ntly of the other hydrogen orunsubstituted or hydroxy- or sulfo-substituted C₁-C₄alkyl; R₁₇ ishydrogen or C₁-C₄alkyl; E is a phenylene radical unsubstituted orsubstituted by C₁-C₄alkyl, halogen, carboxy or by sulfo or is aC₂-C₆alkylene radical; and k is from 1 to 3. R₁₈ and R₁₉ are preferablyhydrogen. E is preferably a phenylene radical unsubstituted orsubstituted by C₁-C₄alkyl, halogen, carboxy or by sulfo. Pc ispreferably the radical of a copper phthalocyanine.

As a radical of a dioxazine dye, A is, for example, a radical of formula

wherein E′ is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical,r, s, v and v′ are each independently of the oth rs the number 0 or 1and Y is as defined hereinabove. Preferably, E′ is C₂-C₄alkylene orunsubstituted or sulfo-substituted 1,3- or 1,4-phenylene, r is thenumber 1, s is the number 0, v is the number 1 and v′ is the number 0 or1.

As a radical of an anthraquinone dye, A is preferably a radical offormula

wherein G is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo, or is acyclohexylene, phenylenemethylene or C₂-C₆alkylene radical, each ofwhich preferably contains at least 2 sulfo groups. G is preferably aphenylene radical unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy or by sulfo.

A is especially a monoazo or disazo chromophor radical of theabove-indicated formula (7a), (7b), (7d), (7e), (7f), (7k), (7o), (7q)or (7t), a formazan radical of the above-indicated formula (8b), or ananthraquinone radical of the above-indicated formula (11).

In the meanings given for the variables, C₁-C₄alkyl is generally methyl,ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl. C₁-C₄Alkoxy isgenerally methoxy, ethoxy, n- or iso-propoxy or n-, iso-, sec- ortert-butoxy. Halogen is generally, e.g., fluorine, chlorine or bromine.Examples of C₁-C₄alkoxycarbonyl are methoxycarbonyl and ethoxycarbonyl.Examples of C₁-C₄alkanoyl are acetyl, propionyl and butyryl. Examples ofC₂-C₄alkanoylamino are acetylamino and propionylamino. Examples ofC₁-C₄hydroxyalkoxy are hydroxymethoxy, β-hydroxyethoxy and β- andγ-hydroxypropoxy. Examples of C₁-C₄sulfatoalkoxy are sulfatomethoxy,β-sulfatoethoxy and β- and γ-sulfatopropoxy.

The reactive dyes of formula (1) contain at least one, preferably atleast two and especially from 2 to 8, sulfo groups, each of which iseither in the form of its free acid or preferably a salt thereof. Assalts there come into consideration, for example, the alkali metal,alkaline arth metal and ammonium salts, salts of an organic amine andmixtures thereof. As examples there may be mentioned sodium, lithium,potassium and ammonium salts, the salt of mono-, di- or tri-ethanolamineand Na/Li and Na/Li/NH₄ mixed salts.

The reactive dyes of formula (1) can be obtained in a manner known perse, such as in the manner described, for example, in U.S. Pat. No.5,989,297, for example as follows:an amino compound of formula A-NH—R₁  (12),a diamine of formula R₂—HN—B—NH—R₃  (13),a compound of formula T-H  (14) anda compound of formula

are reacted with one another in any sequence, in which formulae B, A,R₁, R₂, R₃, T, V₁, V₂, X₁ and X₂ are each as defined hereinabove. Oneprocess variant comprises condensing one of the compounds of formulae(12) and (14) first of all with a compound of formula (15a) or (15b),condensing the condensation product with a diamine of formula (13) andreacting the resulting reaction product with the other compound offormula (12) or (14) which has be n condensed beforehand with thecompound of formula (15a) or (15b).

The condensation reactions between the compounds of formulae (12), (13),(14), (15a) and (15b) are generally carried out analogously to knownprocedures, usually in aqueous solution at temperatures of, for example,from 0 to 50° C. and a pH value of, for example, from 4 to 10. Thecompounds of formulae (12), (13) and (14), as well as the heterocyclichalogen compounds of formulae (15a) and (15b), are known or can beprepared analogously to known compounds.

The end product may optionally in addition be subjected to a conversionreaction. Such a conversion reaction is, for example, the conversion ofa vinylatable reactive group present in T into its vinyl form bytreatment with dilute sodium hydroxide solution, for example theconversion of the β-sulfatoethylsulfonyl or β-chloroethylsulfonyl groupinto the vinylsulfonyl radical. Such reactions are known per se.

In the method according to the invention there are used for theprinting, for example, pastes, that is to say aqueous solutionsthickened and adjusted to the desired consistency by a thickener.

There may be used as thickeners the customary thickeners of natural orsynthetic origin suitable for reactive printing, e.g. alginatethickeners, starch ethers or locust bean flour ethers, cellulosederivatives, e.g. cellulose ethers, such as methylcellulose,ethylcellulose, hydroxyethylcellulose, methylhydroxyethylcellulose,hydroxypropyl cellulos, hydroxypropyl methylcellulose, carboxymethylcllulose, carboxyethylcellulose or cyanoethylcellulose, or a celluloseester, e.g. acetylcellulos. Preference is given to the use in the printpastes of sodium alginate alone or in admixture with modified cellulose,especially with preferably from 20 to 25% by weightcarboxymethylcellulose.

The amount of thickener in the print paste can vary within wide limitsaccording to the desired viscosity. Preferably, the amount of thickenerpresent in the print paste is from 5 to 100 g/kg of print paste,especially from 10 to 80 g/kg of print paste, more especially from 10 to60 g/kg of print paste.

The viscosity of the print paste is generally from 1000 to 20 000 mPa s.Preference is given to the use of print pastes having a viscosity offrom 2500 to 15 000 mPa s, especially from 4000 to 6000 mPa s.

The print pastes may comprise fixing alkalis for the purpose of fixingthe reactive dyes. As compounds having an alkaline reaction there areused, for example, sodium carbonate, sodium hydroxide, disodiumphosphate, trisodium phosphate, sodium acetate, sodium propionate,sodium hydrogen carbonate, borax, aqueous ammonia or alkali donors, e.g.sodium chloroacetate or sodium formate. It is also possible to use asfixing alkali a mixtur of water glass and a 25% aqueous sodium carbonatesolution. The pH value of the additives comprising fixing alkali isgenerally from 7.5 to 13.2, preferably from 8.5 to 12.5. For thepreparation of the print paste, the amount of fixing alkali is soselected that the pH value of the ready-to-use print paste is generallyin the alkaline range, preferably in the range from 7.5 to 12.

Print pastes that do not comprise fixing alkali can be applied accordingto the so-called two-phase printing method, in which the fibre materialis first printed with a print paste without alkali or alkali donor, andthe printed fibre material is dried and then treated with an optionally,thickened aqueous liquor comprising the fixing alkali. Alternatively,the fibre material to be printed can first be treated with an aqueousalkali liquor and then the treated and optionally dried fibre materialprinted with a print paste that does not comprise alkali or alkalidonor.

The print past may also comprise, in addition to the reactiv dyes andthickeners, further customary additives, e.g. preservatives, sequstering agents, emulsifiers, water-insoluble solvents, oxidising agents,reduction inhibitors, antifoams or de-aerators.

There come into consideration as preservatives especiallyformaldehyde-yielding agents, e.g. paraformaldehyde and trioxane,especially aqueous, for example 30 to 40% by weight, formaldehydesolutions; as sequestering agents, for example, nitrilotriacetic acidsodium salt, ethylenediaminetetraacetic acid sodium salt, especiallysodium polymetaphosphate, more especially sodium hexametaphosphate; asemulsifiers especially adducts of an alkylene oxide and a fatty alcohol,more especially an adduct of oleyl alcohol and ethylene oxide; aswater-insoluble solvents high-boiling, saturated hydrocarbons,especially paraffins having a boiling range of approximately from 160 to210° C. (so-called white spirits); and as oxidising agents, for example,an aromatic nitro compound, especially an aromatic mono- ordi-nitro-carboxylic acid or -sulfonic acid, which is optionally presentin the form of an alkylene oxide adduct, especially anitrobenzenesulfonic acid.

As reduction inhibitors there come into consideration, for example,aromatic nitro compounds, especially salts of aromatic mono- ordi-nitro-carboxylic acids or -sulfonic acids, which are optionally inthe form of alkylene oxides, especially alkali metal salts of anitro-benzenesulfonic acid, e.g. 4-nitrobenzenesulfonic acid sodiumsalt. The reduction inhibitor is preferably used in an amount of from0.1 to 4% by weight, especially from 0.8 to 2% by weight, based on thetotal weight of the finished print paste.

There may be used as de-aerator any commercially available de-aeratorprovided that it does not adversely affect the rheological properties ofthe print paste. Preference is given, on account of their goodanti-foaming properties, to low-silicone oil or silicone oil-freede-aerators, which generally contain from 0 to 5% by weight of aconventional silicone oil. Of prime interest are de-aerators thatcomprise as active substance a higher alcohol, such as 2-ethyl-n-hexanolor 2-hexyldecanol, or a mixture thereof with high-boiling hydrocarbonmixtures, and that comprise silicone oils in the amount indicated above.The print paste comprises the de-aerator in an amount of, for example,from 0 to 5% by weight, preferably from 0.1 to 1% by weight, bas d onthe total weight of the finished print paste.

The print pastes may comprise as further additives solubilisers, such asurea, ε-caprolactam, ethylene glycol, diethylene glycol, thiodiethyleneglycol, polyethylene glycol, pentaerythritol, acetin (mixture of glycolmono-, di- and tri-acetate) or dicyandiamide.

When printing on fibre materials, the print paste is applied directly tothe fibre material over the entire surface or over parts thereof, theprinting machines used advantageously being of customary construction,e.g. gravure printing machines, rotary screen printing machines and flatscreen printing machines. The method according to the invention is usedespecially advantageously in screen printing.

As cellulosic fibre materials there come into consideration materialsthat consist wholly or partially of cellulose. Examples include naturalfibre materials, such as cotton, linen and hemp, regenerated fibrematerials, e.g. viscose, polynosic and cuprammonium silk, and cellulosicblends, e.g. cotton/polyester materials. Mainly, woven fabrics, knittedfabrics or webs of such fibres are used.

The fibre material is advantageously dried after the printing procedure,preferably at temperatures of up to 180° C., especially from 125 to 150°C. A fixing process step customarily carried out subsequent thereto inorder to complete the printing and fix the dye, such as steaming of theprinted and dried fabric, is not necessary in the method according tothe invention. After the printing procedure, the fibre material ispreferably dried for from 30 to 120 seconds at from 125 to 150° C.,especially from 140 to 150° C.

The printed and dried fibre material is washed off in conventionalmanner in order to remove unfixed dye. For that purpose the fibrematerial is treated, for example, at from 40° C. to boiling temperaturewith water to which a soap or a synthetic detergent may optionally beadded.

The prints on cellulosic fibre materials obtainable according to themethod of the invention exhibit good allround properties; for examplethey have a high fibre-dye binding stability in both the acidic and thealkaline range, especially the acidic range, a good fastness to light,good wet-fastness properties, such as fastness to washing, to water, tosea water, to cross-dyeing and to perspiration, a good fastness tochlorine, fastness to rubbing, fastness to ironing and fastness topleating, and are distinguished especially by sharp contours, a hightinctorial strength and brilliant colour shades. The degree of fixing ishigh and unfixed dye can readily be washed off, that is to say thesoaping loss is very small.

Some of the reactive dyes of formula (1) are novel. The presentinvention accordingly relates also to reactive dyes of formula (1)indicated hereinabove wherein

-   B is C₂-C₁₂alkylene that may be interrupted by 1, 2 or 3 members    from the group —NH—,-   —N(CH₃)— and —O— and that is unsubstituted or substituted by    hydroxy, sulfo, sulfato, cyano or by carboxy, and-   A, R₁, R₂, R₃, X₁, X₂, T, V₁ and V₂ have the definitions and    preferred meanings given hereinabove,    with the exception of the dyes of formulae

As bridging member B in the reactive dyes according to the invention,preference is given to a C₂-C₁₂alkylene radical that may be interruptedby 1, 2 or 3 members —O— and that is unsubstituted or substituted byhydroxy, sulfo, sulfato, cyano or carboxy.

As bridging member B in the reactive dyes according to the invention,preference is given especially to a C₂-C₁₂alkylene radical, especially aC₂-C₆alkylene radical, e.g. 1,2-ethylene, 1,3-propylene, 1,2-propylene,1,4-butylene, 1,3-butylene, 1,5-pentylene, 3,5-pentylene, 1,6-hexylene,2,5-hexylene, 4,6-hexylene or a radical of formula

which may be interrupted by 1, 2 or 3 members —O— and is unsubstitutedor substituted by hydroxy or sulfato, but is preferably not interruptedby —O—.

As bridging member B in the reactive dyes according to the invention,preference is given more especially to bridging members of formula—CH₂—CH(R₇)— or —(R₇)CH—CH₂—, wherein R₇ is C₁-C₄alkyl, especiallymethyl, and very especially to 1,2-propylene.

The novel reactive dyes can be obtained in a manner known per se, forexample according to the process described above.

The present invention relates also to print pastes that comprise thereactive dyes of formula (1) according to the invention. The printpastes may also comprise, in addition to the reactive dyes according tothe invention, to water and to a thickener, further additives, e.g. theadditives described hereinabove. As thickeners there come intoconsideration, e.g., th thickeners described hereinabove.

The following Examples serve to illustrate the invention. Unlessotherwise indicated, the temperatures are given in degrees Celsius,parts are parts by weight and percentages relate to percent by weight.Parts by weight relate to parts by volume in a ratio of kilograms tolitres.

PREPARATION EXAMPLES 1 TO 94 Example 1

a) 25.3 parts of 4-(β-sulfatoethylsulfonyl)aniline are dissolved in 200parts of water at pH 5 by adding sodium hydroxide. The solution isbuffered with 0.5 part of sodium tripolyphosphate and 150 parts of iceare added. 12.2 parts of trifluorotriazine are added dropwise, withstirring, over a period of from 5 to 10 minutes to that mixture, in thecourse of which the pH is maintained at 5.5 by the addition of anaqueous sodium hydroxide solution and the temperature is maintained atfrom 0 to 2° C. 420 parts of a suspension are obtained.

b) 9.7 parts of trichlorotriazine are dispersed in an ice/water mixtureat 0° C. with the addition of a wetting agent. Over a period of onehour, a neutral solution of 27.3 parts of the aminoazo compound offormula

in 200 parts of water is added dropwise to the resulting solution atfrom 0 to 2° C. and pH 4.5, and stirring is carried out for a furtherhour at 5° C. To the solution obtained there is added dropwise over aperiod of 20 minutes, at pH 5.5, a solution of 4.8 parts of1,2-propylene-diamine in 100 parts of water neutralised with 12.5 partsof concentrated hydrochloric acid. Stirring is then carried out forseveral hours at from 35 to 45° C. and pH 5.5.

c) The suspension obtained according to b) is adjusted to pH 7.5 to 8and added over a period of 30 minutes at pH 7.5 to the suspensionobtained in accordance with a). To complete the reaction, one hour isallowed for the reactants to react fully. The pH of the resultingreaction mixture is then adjusted to 10.5 and stirring is carried outfor 30 minutes. The reaction solution is freed of inorganic salts bydialysis and concentrated by evaporation to yield 86.5 parts of a dyewhich, in the form of the free acid, corresponds to formula

wherein B is the radical of formula

The dye yields prints on cellulose in a yellow shade having goodallround properties.

Example 2

a) 11 parts of cyanuric chloride are stirred at a temperature ofapproximately 0° C. in 50 parts of water with the addition of a wettingagent and 5 parts of disodium hydrogen phosphate. A neutral solution of40 parts of the aminoazo compound of formula

in 400 parts of water is added dropwise, in the course of which the pHvalue is maintained at 4.5 by the addition of aqueous sodium hydroxidesolution. When the condensation is complete, the primary condensationproduct of cyanuric chloride and the aminoazo compound is obtained.

b) 14 parts of cyanuric fluoride are added dropwise at a temperature offrom 0 to 2° C. to a neutral solution of 26 parts of4-(β-sulfatoethylsulfonyl)aniline and 5 parts of disodium hydrogenphosphate in 170 parts of water and the pH value is kept constant by theaddition of aqueous sodium hydroxide solution. A neutral solution of 7.4parts of 1,2-diaminopropane in 30 parts of water is so added dropwise tothe resulting solution of the condensation product of cyanuric fluorideand 4-(β-sulfatoethylsulfonyl)aniline that the pH value does not exceed6. That pH value is maintained until the condensation is complete by theaddition of aqueous sodium hydroxide solution, and towards the end ofthe reaction the reaction solution is h ated to 40° C.

c) The reaction mixture obtained in accordance with a) is added to thereaction mixture obtained in accordance with b) and the pH value isincreased to 8.5, where it is maintained until the condensation iscomplete by the addition of aqueous sodium hydroxide solution. Thereaction solution is freed of inorganic salts by dialysis andconcentrated by evaporation to yield a dye which, in the form of thefree acid, corresponds to formula

wherein B is the radical of formula

The dye yields prints on cellulose in a brilliant yellow shade havinggood allround properties.

Example 3

a) 14 parts of cyanuric fluoride are added dropwise at a temperature offrom 0 to 2° C. to a neutral solution of 40 parts of the aminoazocompound specified in Example 2 a) and 5 parts of disodium hydrogenphosphate in 400 parts of water, and the pH value is kept constant bythe addition of aqueous sodium hydroxide solution. When condensation iscomplete, the primary condensation product of cyanuric fluoride and theaminoazo compound is obtained.

b) The reaction mixture obtained in accordance with a) is added to thereaction mixture obtained in accordance with Example 2 b) and the pH isincreased to a value of 8.5, where it is maintained until thecondensation is complete by the addition of aqueous sodium hydroxidesolution. The reaction solution is freed of inorganic salts by dialysisand concentrated by evaporation to yield a dye which, in the form of thefree acid, corresponds to formula

wherein B is the radical of formula

The dye yields prints on cellulose in a brilliant yellow shade havinggood allround properties.

Examples 4 to 28

Proceeding analogously to one of the procedures described in Examples 1to 3, it is possible to obtain the reactive dyes of formula

wherein A and B each have the definitions given in Table 1. The dyesyield prints on cellulose in the colour shades indicated having goodallround properties.

TABLE 1 Example A B Shade 4

yellow 5

yellow 6

yellow 7

red 8

scarlet 9

red 10

red 11

yellow 12

brown 13

yellow 14

red 15

orange 16

orange 17

scarlet 18

orange 19

orange 20

navy 21

navy 22

navy 23

blue 24

scarlet 25

scarlet 26

blue 27

blue 28

grey 1:2 Cr complex

Examples 29 to 33

Proceeding analogously to one of the procedures described in Examples 1to 3, it is possible to obtain the reactive dyes of formula

wherein A, X₁, X₂ and

each have the definitions given in Table 2. The dyes yield prints oncellulose in the colour shades indicated having good allroundproperties.

TABLE 2 Example A X₁/X₂

Shade 29

F/F

blue 30

Cl/F

orange 31

Cl/F

yellow 32

F/F

blue 33

Cl/Cl

yellow

Examples 34 to 60

Proceeding analogously to the procedure described in Example 1, butusing instead of 25.3 parts of 4-(β-sulfatoethylsulfonyl)aniline anequimolar amount of one of the amines of formula D_(xy)—NH₂ set out inTable 3, reactive dyes of the general formula

are obtained wherein B is the radical of formula

and D_(xy) has the definition of the radical given in each case in Table3. The dyes yield prints on cellulose in a yellow shade having goodallround properties.

TABLE 3 Amine Example D_(xy)—NH₂ D_(xy) 34 D₁₀—NH₂

35 D₁₁—NH₂

36 D₁₂—NH₂

37 D₁₃—NH₂

38 D₁₄—NH₂

39 D₁₅—NH₂

40 D₁₆—NH₂

41 D₁₇—NH₂

42 D₁₈—NH₂

43 D₁₉—NH₂

44 D₂₀—NH₂

45 D₂₁—NH₂

46 D₂₂—NH₂

47 D₂₃—NH₂

48 D₂₄—NH₂

49 D₂₅—NH₂

50 D₂₆—NH₂

51 D₂₇—NH₂

52 D₂₈—NH₂

53 D₂₉—NH₂

54 D₃₀—NH₂

55 D₃₁—NH₂

56 D₃₂—NH₂

57 D₃₃—NH₂

58 D₃₄—NH₂ D₃₄ = —NH—(CH₂)₂—SO₂—(CH₂)₂—Cl 59 D₃₅—NH₂ D₃₅ =—NH—(CH₂)₃—SO₂—(CH₂)₂—Cl 60 D₃₆—NH₂ D₃₆ =—NH—(CH₂)₂—O—(CH₂)₂—SO₂—(CH₂)₂—Cl

Examples 61 to 63

Proceeding analogously to one of the procedures described in Examples 1to 3, it is possible to obtain the reactive dyes of the formulaeindicated below wherein B is the radical of formula

The dyes yield prints on cellulose in the colour shades indicated havinggood allround properties.

Examples 64 to 94

Analogously to the procedure described in Examples 1 to 3, it ispossible to obtain the reactive dyes of formula

wherein A and B each have the definitions given in Table 4. The dyesyield prints on cellulose in the colour shades indicated having goodallround properties.

TABLE 4 Example A B Shade 64

yellow 65

yellow 66

yellow 67

yellow 68

orange 69

red 70

yellow 71

yellow

72

orange 73

orange 74

orange 75

scarlet 76

scarlet

77

red 78

red 79

red 80

red 81

red 82

brown 83

navy 84

navy

85

navy

86

blue 87

grey 1:2 Cr complex 88

turquoise 89

blue 90

yellow 91

yellow 92

orange 93

—(CH₂)₃—O—(CH₂)₄—O—(CH₂)₃— red 94

—CH₂—CH₂— yellow

Method Examples 95 to 98 Example 95

Mercerized sateen fabric is printed with a print paste containing per kgof print paste

-   30 g of the dye from Example 1,-   100 g of urea,-   20 g of sodium carbonate,-   500 g of a commercial alginate thickener (®Lamitex M5 6%) and-   3 g of antifoam (®Lyoprint AP).

The print is dried for 120 seconds at 150° C. and then rinsed with coldwater, washed off in boiling water, rinsed with cold water again anddried.

A yellow print having good allround properties is obtained.

Example 96

By proceeding as indicated in Example 95, but using double the amount ofurea, there is likewise obtained a yellow print having good allroundproperties.

By proceeding as indicated in Example 95 or 96, but using instead of 30g of the dye from Example 1 the same amount of a dye from Examples 2 to94, there are likewise obtained prints having good allround propertiesin the shades indicated in each of the corresponding PreparationExamples.

Example 97

Causticized viscose fabric is printed with a print paste containing perkg of print paste

-   30 g of the dye from Example 1,-   100 g of urea,-   20 g of sodium carbonate,-   500 g of a commercial alginate thickener (®Lamitex M5 6%) and-   3 g of antifoam (®Lyoprint AP).

The print is dried for 120 seconds at 150° C. and then rinsed with coldwater, washed off in boiling water, rinsed with cold water again anddried.

A yellow print having good allround properties is obtained.

Example 98

By proceeding as indicated in Example 97, but doubling the amount ofurea, there is likewise obtained a yellow print having good allroundproperties.

By proceeding as indicated in Example 97 or 98, but using instead of 30g of the dye from Example 1 the same amount of a dye from Examples 2 to94, there are likewise obtained prints having good allround propertiesin the shades indicated in each of the corresponding PreparationExamples.

1. A reactive dye of formula

wherein A is the radical of a monoazo, polyazo, metal complex azo,anthraquinone, phthalocyanine or dioxazine chromophore, R₁ is hydrogenor unsubstituted or substituted C₁-C₄alkyl, R₂ and R₃ are hydrogen, X₁and X₂ are halogen, B is a radical of formula —CH₂—CH(R₇)— or—(R₇)CH—CH₂—, wherein R₇ is C₁-C₄alkyl, T is a reactive radical offormula

R₄ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy,sulfo, sulfato, carboxy or by cyano, or a radical

wherein R₅ is as defined hereinbelow, R₅ is hydrogen, hydroxy, sulfo,sulfato, carboxy, cyano, halogen, C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy,carbamoyl or a group —SO₂—Y, R₆ is hydrogen or C₁-C₄alkyl, alk and alk₁are each independently of the other linear or branched C₁-C₆alkylene,arylene is an unsubstituted or sulfo-, carboxy-, hydroxy-, C₁-C₄alkyl-,C₁-C₄alkoxy- or halo-substituted phenylene or naphthylene radical, Y isvinyl or a radical —CH₂—CH₂—U and U is a leaving group, Y₁ is a group—CH(Hal)—CH₂(Hal) or —C(Hal)═CH₂, wherein Hal is chlorine or bromine, Wis a group —SO₂—NR₆—, —CONR₆— or —NR₆CO—, wherein R₆ is as definedhereinabove, Q is a radical —O— or —NR₆—, wherein R₆ is as definedhereinabove, n is the number 0 or 1, and V₁ and V₂ are eachindependently of the other N, C—H, C—Cl or C—F.
 2. A print paste,comprising a reactive dye of formula (1) according to claim
 1. 3. Areactive dye according to claim 1, wherein R₁ is hydrogen or C₁-C₄alkyl.4. A reactive dye according to claim 1, wherein X₁ and X₂ are eachindependently of the other chlorine or fluorine.
 5. A reactive dyeaccording to claim 1, wherein one of the radicals X₁ and X₂ is fluorineand the other is chlorine, or X₁ and X₂ are both fluorine.
 6. A reactivedye according to claim 1, wherein T is a group of formula

wherein y is vinyl, β-chloroethy or β-sulfatoethyl.
 7. A reactive dyeaccording to claim 1, wherein V₁ and V₂ are N.
 8. A reactive dyeaccording to claim 1, wherein A is a radical of formula

in which formulae (R₈)₀₋₃ denotes from 0 to 3 identical or differentsubstituents selected from the group consisting of C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo,

wherein (R₉)₀₋₄ denotes from 0 to 4 identical or different substituentsselected from the group consisting of halogen, nitro, cyano,trifluoromethyl, sulfamoyl, carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy, amino,acetylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo,

in which formulae R₁₀ is hydrogen, C₁-C₄alkanoyl, benzoyl or ahalotriazinyl radical of the formula

in which T₁ is a reactive radical of formula

R₄ is hydrogen, C₁-C₄alkyl unsubstituted or substituted by hydroxy,sulfo, sulfato, carboxy or by cyano, or a radical

wherein R₅ is as defined hereinbelow, R₅ is hydrogen, hydroxy, sulfo,sulfato, carboxy, cyano, halogen, C₁-C₄alkoxycarbonyl, C₁-C₄alkanoyloxy,carbamoyl or a group —SO₂—Y, R₆ is hydrogen or C₁-C₄alkyl, alk and alk₁are each independently of the other linear or branched C₁-C₆alkylene,arylene is an unsubstituted or sulfo-, carboxy-, hydroxy-, C₁-C₄alkyl-,C₁-C₄alkoxy- or halo-substituted phenylene or naphthylene radical, Y isvinyl or a radical —CH₂—CH₂—U and U is a leaving group, Y₁ is a group—CH(Hal)—CH₂(Hal) or —C(Hal)═CH₂, wherein Hal is chlorine or bromine, Wis a group —SO₂—NR₆—, —CONR₆— or —NR₆CO—, wherein R₆ is as definedhereinabove, Q is a radical —O— or —NR₆—, wherein R₆ is as definedhereinabove, n is the number 0 or 1, X₂′ is halogen, and R₃′ is hydrogenor unsubstituted or substituted C₁-C₄alkyl,

in which formulae (R₁₁)₀₋₃ denotes from 0 to 3 identical or differentsubstituents selected from the group consisting of C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo,

wherein R₁₂ and R₁₄ are each independently of the other hydrogen,C₁-C₄alkyl or phenyl and R₁₃ is hydrogen, cyano, carbamoyl orsulfomethyl,

wherein (R₁₅)₀₋₂ denotes from 0 to 2 identical or different substituentsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen,carboxy and sulfo; and y is as defined hereinabove,

wherein (R₁₆)₀₋₂ denotes from 0 to 2 identical or different substituentsselected from the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen,carboxy and sulfo, and y has the definitions given hereinabove,

in which formulae (R₈)₀₋₃ denotes from 0 to 3 identical or differentsubstituents selected from the group consisting of C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo, (R₈′)₀₋₃ denotes from 0 to 3identical or different substituents selected from the group consistingof C₁-C₄alkyl, C₁-C₄alkoxy, acetylamino, halogen, carboxy, sulfo,C₁-C₄hydroxyalkoxy and C₁-C₄sulfatoalkoxy, (R₉)₀₋₄ denotes from 0 to 3identical or different substituents selected from the group consistingof halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl,C₁-C₄alkyl, C₁-C₄alkoxy, amino, acetylamino, ureido, hydroxy, carboxy,sulfomethyl and sulfo, (R₁₀′)₀₋₃ denotes from 0 to 3 identical ordifferent substituents selected from the group consisting of C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxy and sulfo, and Y is as definedhereinabove,

wherein Pc is the radical of a metal phthalocyanine; R is —OH and/or—NR₁₈R₁₉; R₁₈ and R₁₉ are each independently of the other hydrogen orunsubstituted or hydroxy- or sulfo-substituted C₁-C₄alkyl; R₁₇ ishydrogen or C₁-C₄alkyl; E is a phenylene radical unsubstituted orsubstituted by C₁-C₄alkyl, halogen, carboxy or by sulfo or is aC₂-C₆alkylene radical; and k is from 1 to 3,

wherein E′ is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, halogen, carboxy or by sulfo or is a C₂-C₆alkylene radical,r, s, v and v′ are each independently of the others the number 0 or 1and Y is as defined hereinabove, or

wherein G is a phenylene radical unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxy or by sulfo, or is acyclohexylene, phenylenemethylene or C₁-C₆alkylene radical, each ofwhich contains at least 2 sulfo groups.